Rolling two-dimensional covalent organic framework (COF) sheets into one-dimensional electronic and proton-conductive nanotubes

• 成果类型: Article
• 署名作者: Li, Zhuowei; Paitandi, Rajendra Prasad; Tsutsui, Yusuke; Matsuda, Wakana; Nobuoka, Masaki; Chen, Bin; Ghosh, Samrat; Tanaka, Takayuki; Suda, Masayuki; Zhu, Tong; Kageyama, Hiroshi; Miyake, Yoshihiro; Shinokubo, Hiroshi; Takagi, Makito; Shimazaki, Tomomi; Tachikawa, Masanori; Suzuki, Katsuaki; Kaji, Hironori; Ando, Yasunobu; Ezaki, Takahiro; Seki, Shu
• 署名单位: Kyoto University; Kyoto University; Nagoya University; Yokohama City University; Kyoto University; University of Tokyo
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-14550
• DOI: 10.1073/pnas.2424314122
• 发表日期: 2025-04-22
• 关键词: gas-storage; carbon nanotubes; energy-storage; graphene; crystalline; SEPARATION

摘要

Mimicking the interconvertible carbon allotropes of 2-dimensional (2D) graphene and 1-dimensional (1D) carbon nanotubes (CNTs), herein we report the in situ transformation of 2D it-conjugated covalent organic frameworks (COFs) sheet into 1D nanotubular structures via self-assembly the sheets at solvent interfaces. The facile roll-sheets self-assembly resulted in coaxial nanotubes with uniform cross-sectional diameter, which was realized for diazapyrene-based COFs but not for the corresponding pyrene COF, although both possess similar chemical structures. Upon replacing the carbon atoms at 2,7-positions of pyrene with nitrogen, contrasting optical and electronic properties were realized, reflecting the rolled structure of the conjugated 2D sheets. The nanotubes exhibited concerted electronic-and proton-conducting nature with stable conducting pathways at ambient conditions. The nitrogen centers act simultaneously as the site for charge carrier doping and proton acceptors, as evidenced by the high photo-and electrical conductivity, as well as the record proton conductivity (sigma = 1.98 S cm-1) results. The present diazapyrene-based 1D nanotubular COF serves as a unique materials platform with electronic conduction in the wall and proton conduction in the core, respectively.